Methyl chloroformate → Ethyl 6-chloro-1H-pyrrolo[2,3-b]pyridine-2-carboxylate

HRID 857455Notes

Reaction equation

HRID 857455 reaction equation
[NH:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][N+:8]=2[O-])[CH:3]=[C:2]1[C:11]([O:13][CH2:14][CH3:15])=[O:12].[Cl:16]C(OC)=O>C1COCC1>[Cl:16][C:7]1[N:8]=[C:9]2[C:4]([CH:3]=[C:2]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[NH:1]2)=[CH:5][CH:6]=1

Participants

4

Reactant 2

HCID 6586Methyl chloroformateHCID 178468513HCID 178468513, compound

Product 1

HCID 21868758Ethyl 6-chloro-1H-pyrrolo[2,3-b]pyridine-2-carboxylateYield 26.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of ethyl 7-azaindole-2-carboxylate-7-oxide (1.32 g, 6.4 mmol) and hexamethyldisilazale (1.4 mL, 6.6 mmol) in THF (30 mL) at 0° C. was added dropwise over 30 min a solution of methyl chloroformate (1.2 mL, 15.5 mmol) in THF (5 mL). The mixture was warmed to room temperature, stirred for 2 h and partitioned between ether (50 mL) and water (50 mL). The aqueous layer was extracted with ether (30 mL). The combined organic extracts were washed (water, brine), dried (sodium sulfate) and purified by column chromatography [SiO2; heptane-ether (3:1)] to give ethyl 6-chloro-7-azaindole-2-carboxylate as a white solid (0.38 g, 26%). mp 144–145° C. Found: C, 53.69; H, 4.05; N, 12.39%. C10H9N2ClO2 requires: C, 53.47; H, 4.04; N, 12.46%.

Workup

  1. custompartitioned between ether (50 mL) and water (50 mL)
  2. extractionThe aqueous layer was extracted with ether (30 mL)
  3. washThe combined organic extracts were washed (water, brine)
  4. dry with materialdried (sodium sulfate)
  5. custompurified by column chromatography [SiO2; heptane-ether (3:1)]

Sources & evidence

ORD record
ord-22f1a90dea4d4b10a3dbc241cfc90e39
Source dataset
uspto-grants-2006_12
Patent number
US07145009B2

Reaction notes

Loading…